Process for forming photographic images by high speed diffusion transfer process

ABSTRACT

In a process for forming photographic images by a high speed diffusion transfer process, the improvement which comprises using a small amount of a highly active developing agent and a large amount of at least one phenol is disclosed.

United States Patent [191 Iwano et al.

[ PROCESS FOR FORMING PHOTOGRAPIIIC IMAGES BY HIGH SPEED DIFFUSION TRANSFER PROCESS [75] Inventors: Haruhiko Iwano; Mitsugu Tanaka;

Tesuo Otsuki; Atsuaki Arai, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: Apr. 20, 1971 [21] Appl. No.: 135,766

[30] Foreign Application Priority Data Apr. 20,1970 Japan 45-33135 [52] 'UIS; Ci. ....'.....'.....T."..T W19 1296766 12/96/664 [51] Int. Cl G03c 5/54 [58] Field of Search 96/29, 66

[ Nov. 19, 1974 [56] References Cited UNITED STATES PATENTS 2,059,889 11/1936 Mannes et al. 96/59 2,652,428 9/1953 Weissberger 96/66 X 3,108,001 10/1963 Green 96/66 3,186,843 6/1965 Haas 96/66 R 3,241,964 3/1966 Land 96/66 R 3,495,983 2/1970 Strange 96/64 Primary Examiner-David Klein Assistant Examiner-John L. Goodrow Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [5 7] ABSTRACT In a process for forming photographic images by a high speed diffusion transfer process, the improvement which comprises using a small amount of a highly active developing agent and a large amount of at least one phenol is disclosed.

12 Claims, No Drawings PROCESS FOR FORMING PHOTOGRAPHIC IMAGES BY HIGH SPEED DIFFUSION TRANSFER PROCESS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for forming photographic images by a high speed diffusion transfer process, and more particularly to a process for treating an exposed silver halide photographic material by a high speed diffusion transfer process.

2. Description of the Prior Art In diffusion transfer processes, for the formation of positive silver images, a latent image contained in a selectively exposed light-sensitive silver halide emulsion is developed. Almost concurrently therewith, a soluble silver complex is obtained by reaction of a silver halide solvent with the unexposed and undeveloped silver halide of said emulsion. Preferably, the light-sensitive silver halide emulsion is developed with a processing composition in a viscous condition, which is spread between the light-sensitive element comprising the silver halide emulsion and an image-receiving element comprising a suitable silver precipitating layer. The processing composition effects development of the latent image in the emulsion and substantially contemporaneous therewith forms a soluble complex, for example, a thiosulfate or thiocyanate complex, with the undeveloped silver halide. This soluble silver complex is, at least in part, transported in the direction of the imagereceiving element and the silver thereof is largely precipitated in the silver precipitating layer of said element to form the desired positive images therein.

High speed diffusion transfer processes are generally of the type in which, for example, a silver halide emulsion layer containing a latent image formed by exposure and an image-receiving layer, in superposition, are subjected to a processing composition containing a highly energetic silver halide developing agent and a silver halide solvent in order to form a silver transfer image in and/or on the image-receiving layer.

The silver halide solvent reacts with unreduced silver halide to form the soluble silver complex which, in turn, is reduced in the presence of the image-receiving layer to form the desired positive images. The lightsensitive layer may be subsequently dissociated or stripped from the image-receiving layer.

An object of the present invention is to provide novel high speed diffusion transfer processes wherein a silver halide emulsion has been subjected to the minimum exposure, for example, A.S.A. Exposure Index of 1,000

or more and developed with a combination of two types of developing agents to form good positive images.

Another object of the present invention is to provide novel high speed diffusion transfer processes wherein the stripping properties of the developing solutions from the image-receiving layer having positive images are improved and good positive images are obtained in 1 minute or less.

A further object of the present invention is to provide a novel developing solution for high speed diffusion transfer processes.

SUMMARY OF THE INVENTION It has now been found that a combination of a highly active developing agent and phenol or a derivative thereof as alow active developing agent may be employed to attain the above objects.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to attain any of the above objects, two types of developing solutions have been proposed; one type is a treating solution containing a kind of developing agent having high activities (hereinafter, referred to as a highly active developing agent), by which a latent image contained in a light-sensitive silver halide emulsion exposed .to the minimum exposure is developed and a positive image is simultaneously formed on a image receiving layer, and the other is a developing solution containing a highly active developing agent capable of developing an exposed silver halide emulsion strongly and a low active developing agent capable of reducing a soluble silver complex and forming a positive image on an image-receiving layer.

The process of the present invention belongs to the latter type but the process of the present invention is characterized by using phenols as the low active developing agent in combination with the highly active developing agent.

The phenols used as a low active developing agent may contain phenol and phenol derivative. Asthe phenol derivatives, there are phenols substituted with an alkyl group having 1 to 4 carbon atoms, and alkenyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, a halogen atom, a nitro group, a cyano group, a nitroso group, a carboxy] group,a carboalkoxy group, of which the alkoxy group has 1 to 4 carbon atoms, a sulfo group, an acyl group, an acyloxy group and/or other groups. These substituents may be substituted with each other.

The phenol derivative has 1 to 3 substituents, which may be connected to the 0-, m-, or p-position of the phenol.

The practical examples of phenols employedin the process are;

phenol cresol (including 0-, mand p-isomers) 2,6-dimethylphenol 2,3,S-trimethylphenol 2-allylphenol Z-methoxyphenol 0,0'-dihydroxybiphenyl 2-chlorophenol 2-hydroxylmethylphenol 4-B-aminomethylphenol 4-nitrophenol 3-cyanophenol 4-nitrosophenol salicylic phenol 4-acetylphenol The highly active developing. agents used together with the phenols are aminophenols such as paminophenol or N-methyl-p-aminophenol sulfate.

In the process of the present invention, it is preferable that a small amount of the highly active developing agent and a large amount of the low active developing agent be used. The amount of the latter must be substantially more than that of the former. More particularly, the amount of the highly active developing agent is not more than 0.2 mol/liter and that of the low active developing agent is not less than 0.1 mol/liter, preferably not less than 0.3 mol/liter.

Further, the developing solution of the present invention may contain a silver halide solvent such as thiosulfate or thiocyanate, an alkali agent such as sodium hydroxide and a viscosity-imparting agent such as carboxymethyl cellulose or hydroxyethyl cellulose.

The concentration of the alkali agent, or the pH of the developing solution may be a conventional value, for example, 2 to 5 percent alkali. The viscosity of the developing solution may be 1,000 to 200,000, preferably 5,000 to 50,000.

- The technical conception that a combination of a highly active developing agent and a low active developing agent should be employed in the treatment processing of a high speed diffusion transfer process has already been suggested, for example, in Japanese Patent Publication No. 19, 194/69. In this Publication, however, the low active developing agents are restricted to hydroxylamines or ascorbic acids, which have been known as developing agents. The present invention, on the other hand, is novel in using phenols which have never been considered as developing agents. In fact, the phenols dont agree with KEN- DALLs Law concerning the chemical structural conditions required as developing agents.

Furthermore, we have found that, by using phenols, there may be obtained positive images which are superior, for example, in gradation and that, when the positive image is removed from the silver halide emulsion layer (negative layer) and the developing solution layer after the diffusion transfer processing, the developing solution is neither deposited nor remained on the surface of the positive image, and therefore the stripping property of the solution is improved. As the result of this improvement, there may be attained a number of advantages; for example, appearance of gloss on the surface of positive images and simplification of the working-up process after the diffusion transfer process- In the specification of U.S. Pat. No. 3,186,843, are described phenols for use as developing agents, but the phenols described therein are substituted with substituents in the 2-, 4- and 6- positions, especially the substituents in the 2- and 4- positions, having a sterically large structure, and must be employed mainly in a nonaqueous solvent. On the other hand, the phenols of the present invention are highly water-soluble as compared with those compounds of the above U.S. Patent, and are used mainly in an aqueous solution. The present invention therefore is evidently different from the U.S. Patent in the purposes and method of the application Therefore the present invention is a quite novel one.

The following examples of the present invention areprovided.

Example 1 Between the silver halide emulsion layer exposed in the region of such low illuminance as more than ASA 1,000, and an image-receiving layer comprising a silver-precipitant layer containing nuclei of physical development, a developing solution of the following composition was uniformly spread in a thickness of about 30 microns to effect the diffusion transfer processing.

After a contact time of about 30 seconds, the imagereceiving layer was stripped, and there was obtained a glossy positive image with satisfactory gradation and without any developing solution remained.

Composition of the above-described processing solution.

Water 1.000 ml. Carboxymcthyl cellulose 40.0 g. Na SO 60.0 g. Na S O 40.0 g. N-methyl-p-aminophenol sulfate 0.1 molc p-Cresol 0.5 mole Example 2 Repeating the same processing as in Example 1 but using 0.5 mol/liter of 2-methoxyphenol instead of pcresol, there was obtained a glossy positive image of satisfactory gradation.

Example 3 Repeating the same processing as in Example 1 but using 0.5 mol/liter of 2, 6-dimethylphenol instead of pcresol, there was obtained a glossy positive image of satisfactory gradation.

Example 4 Repeating the same processing as in Example 1 but using 2-chlorophenol in an amount of 0.5 mol per liter instead of p-cresol, a glossy positive image having a satisfactory gradation was obtained.

Example 5 Repeating the same processing as in Example 1 except that p-cresol was replaced by 0.5 mol per liter of 4-nitrophenol, there was obtained a glossy positive image of satisfactory gradation.

Example 6 Repeating the same processing as in Example 1 but using 4-acetlyphenol instead of p-cresol, there was obtained a glossy positive image of satisfactory gradation.

This invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that various variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

What is claimed is:

1. In a process for forming photographic images by a high speed silver halide diffusion transfer process, the improvement which comprises using an aqueous developer containing a small amount of a highly active silver halide developing agent and a large amount of at least one phenol having substantially no silver halide developing activity.

2. The process as claimed in claim 1, wherein said phenol is phenol or phenol substituted with l to 3 substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, a halogen atom, a nitro group, a cyano group, a nitroso group, a carboxyl group, a carboalkoxy group, of which the alkoxy group group, an acyl group 2-allylphenol, 2-methoxyphenol, 0, 0 dihydroxybiphenyl, 2-chlorophenol, 2- hydroxymethylphenol, 4-B-aminoethylphenol, 4-

nitrophenol, 3-cyanophenol, 4-nitrosophenol, salicylic acid or 4-acetylphenol.

7. The process as claimed in claim 1, wherein said developing solution contains a silver halide solvent, an alkali and a viscosity-imparting agent.

8. The process as claimed in claim 7, wherein said silver halide solvent is thiosulfate or thiocyanate.

9. The process as claimed in claim 7, wherein said alkali is sodium hydroxide or potassium hydroxide.

110. The process as claimed in claim 7, wherein said viscosity-imparting agent is carboxymethyl cellulose or hydroxyethyl cellulose.

11. The process as claimed in claim 7, wherein said developing solution has a viscosity of from 1,000 to 200,000.

12. The process as claimed in claim 7, wherein said developing solution contains from 2 to 5 wt. percent 

1. IN A PROCESS FOR FORMING PHOTOGRAPHIC IMAGES BY A HIGH SPEED SILVER HALIDE DIFFUSION TRANSFER PROCESS, THE IMPROVEMENT WHICH COMPRISES USING AN AQUEOUS DEVELOPER CONTAINING A SMALL AMOUNT OF A HIGHLY ACTIVE SILVER HALIDE DEVELOPING AGENT AND A LARGE AMOUNT OF AT LEAST ONE PHENOL DEVELOPING STANTIALLY NO SILVER HALIDE DEVELOPING ACTIVITY.
 2. The process as claimed in claim 1, wherein said phenol is phenol or phenol substituted with 1 to 3 substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, a halogen atom, a nitro group, a cyano group, a nitroso group, a carboxyl group, a carboalkoxy group, of which the alkoxy group has 1 to 4 carbon atoms, a sulfo group, an acyl group and an acyloxy group.
 3. The process as claimed in claim 1, wherein the amount of highly active developing agent is not more than 0.2 mol/liter and the amount of phenol is not less than 0.1 mol/liter.
 4. The process as claimed in claim 1, wherein said highly active developing agent is an aminophenol.
 5. The process as claimed in claim 1, wherein said phenol is phenol or cresol.
 6. The process as claimed in claim 1, wherein said phenol is 2, 6-dimethyl-phenol, 2, 3, 5-trimethylphenol, 2-allyl-phenol, 2-methoxyphenol, 0, 0''-dihydroxybiphenyl, 2-chlorophenol, 2-hydroxymethylphenol, 4- Beta -aminoethylphenol, 4-nitrophenol, 3-cyanophenol, 4-nitrosophenol, salicylic acid or 4-acetylphenol.
 7. The process as claimed in claim 1, wherein said developing solution contains a silver halide solvent, an alkali and a viscosity-imparting agent.
 8. The process as claimed in claim 7, wherein said silver halide solvent is thiosulfate or thiocyanate.
 9. The process as claimed in claim 7, wherein said alkali is sodium hydroxide or potassium hydroxide.
 10. The process as claimed in claim 7, wherein said viscosity-imparting agent is carboxymethyl cellulose or hydroxyethyl cellulose.
 11. The process as claimed in claim 7, wherein said developing solution has a viscosity of from 1,000 to 200,000.
 12. The process as claimed in claim 7, wherein said developing solution contains from 2 to 5 wt. percent alkali. 